Patent application title: COMPOSITION, ARTICLE, AND ASSOCIATED METHOD

Abstract:

A composition includes a post-cured polymer. A post-cured polymer includes
a reaction product of a first cycloolefin and a metathesis catalyst
having ruthenium, osmium, or both ruthenium and osmium. The post-cured
polymer has a glass transition temperature in a range that is greater
than 340 degrees Celsius. An associated article and a method are also
provided.

Claims:

1. A composition, comprising:a post-cured polymer formed from a polymer
that is reaction product of:a first cycloolefin; anda metathesis catalyst
comprising ruthenium, osmium, or both ruthenium and osmium,wherein the
post-cured polymer has a glass transition temperature in a range that is
greater than 340 degrees Celsius.

2. The composition as defined in claim 1, wherein the post-cured polymer
has a glass transition temperature in a range that is greater than about
400 degrees Celsius.

3. The composition as defined in claim 1, wherein the post-cured polymer
has been post-cured at a temperature that is greater than about 325
degrees Celsius.

4. The composition as defined in claim 1, wherein the post-cured polymer
has been post-cured at a temperature that is greater than about 350
degrees Celsius.

5. The composition as defined in claim 1, wherein the post-cured polymer
has a storage modulus in a range that is greater than about
5.times.10.sup.9 dynes/cm2 at about 350 degrees Celsius.

6. The composition as defined in claim 1, wherein the first cycloolefin is
a monofunctional cycloolefin.

7. The composition as defined in claim 1, wherein the first cycloolefin
comprises a structure having a formula (I): ##STR00005## wherein "v" is
1, 2, 3, 4, 5, or 6;R1 is independently at each occurrence hydrogen,
a halogen atom, an aliphatic radical, a cycloaliphatic radical, an
aromatic radical, an alkoxy group, a hydroxy group, an ether group, an
aldehyde group, an ester group, a ketone group, a thiol group, a
disulfide group, an amine group, an amide group, a quaternary amine
group, an imine group, an isocyanate group, a carboxyl group, a silanyl
group, a phosphanyl group, a sulfate group, a sulfonate group, a nitro
group, or two or more R1 together form a cycloaliphatic radical, an
aromatic radical, an imide group, or a divalent bond linking two carbon
atoms; andY is C(R2)2, C═C(R2)2,
Si(R2)2, O, S, NR2, PR2, BR2, or AsR2,
wherein R2 is independently at each occurrence hydrogen, an
aliphatic radical, a cycloaliphatic radical, or an aromatic radical.

8. The composition as defined in claim 1, wherein the first cycloolefin
comprises one or more of dicyclopentadiene, norbornene, oxanorbornene,
norbornadiene, cyclooctadiene, cyclooctene, cyclotetraene, cyclodecene,
cyclododecene, or a derivative thereof.

9. The composition as defined in claim 1, wherein the metathesis catalyst
comprises a structure having a formula (III): ##STR00006## wherein "a"
and "b" are independently integers from 1 to 3, with the proviso that
"a+b" is less than or equal to 5;M is ruthenium or osmium;X is
independently at each occurrence an anionic ligand;L is independently at
each occurrence a neutral electron donor ligand;R6 is hydrogen, an
aliphatic radical, a cycloaliphatic radical, or an aromatic
radical;R7 is an aliphatic radical, a cycloaliphatic radical, an
aromatic radical, or S--R8; or R6 and R7 together form a
cycloaliphatic radical or an aromatic radical; andR8 is an aliphatic
radical, a cycloaliphatic radical, or an aromatic radical.

10. An article, comprising the composition as defined in claim 1 and a
filler.

11. The article as defined in claim 10, wherein the filler comprises one
or more material selected from the group consisting of siliceous
materials, carbonaceous materials, metal hydrates, metal oxides, metal
borides, and metal nitrides.

12. The article as defined in claim 10, wherein the filler comprises a
fibrous material comprising a carbon fiber or a polymer fiber.

13. The article as defined in claim 10, wherein the filler comprises a
fibrous material comprising a glass fiber or a ceramic fiber.

14. The article as defined in claim 10, wherein the filler is present in
an amount in a range of from about 20 weight percent to 85 weight percent
of the article.

15. The article as defined in claim 10, comprising a coupling agent
composition.

16. A composition comprising a post-cured polymer that results from a
metathesis polymerization of a first cycloolefin initiated by a
metathesis catalyst to form a polymer, and a post-curing of the polymer
at a temperature that is greater than an onset temperature for a
secondary curing reaction of the polymer.

17. The composition as defined in claim 16, wherein post-curing the
polymer at a temperature that is greater than onset temperature results
in an increase in glass transition temperature of the post-cured polymer
by greater than about 200 degrees Celsius.

18. The composition as defined in claim 16, wherein the onset temperature
is greater than about 325 degrees Celsius.

19. The composition as defined in claim 16, wherein the post-cured polymer
has a glass transition temperature that is greater than about 400 degrees
Celsius.

20. A composition, comprising a post-cured polymer formed from a polymer
that is a reaction product of:a first cycloolefin; anda metathesis
catalyst,wherein the post-cured polymer has a glass transition
temperature that is greater than 340 degrees Celsius, and the post-cured
polymer has an olefinic carbon content that is less than about 35
percent.

21. The composition as defined in claim 20, wherein the post-cured polymer
has an olefinic carbon content that is less than about 30 percent.

22. A method, comprising:initiating a metathesis polymerization of a first
cycloolefin by a metathesis catalyst to form a polymer; andpost-curing
the polymer at a temperature that is greater than an onset temperature
for a secondary curing of the polymer.

23. The method as defined in claim 22, comprising post-curing the
resulting polymer at a temperature that is greater than about 325 degrees
Celsius.

24. The method as defined in claim 22, comprising contacting a filler with
a curable composition comprising the first cycloolefin and the metathesis
catalyst.

25. The method as defined in claim 22, comprising impregnating a fibrous
material with a curable composition comprising the first cycloolefin and
the metathesis catalyst.

Description:

BACKGROUND

[0001]1. Technical Field

[0002]The invention includes embodiments that relate to a
cycloolefin-based post-cured composition and article formed therefrom.
The invention includes embodiments that relate to a method of making the
cycloolefin-based post-cured composition and article.

[0005]However, currently available polycycloolefin compositions and
composites may exhibit low glass transition temperature (Tg).
Further, these materials may lack a desirable level of dimensional
integrity or stiffness when subjected to elevated temperatures, which may
limit the use of these materials in high temperature applications.

[0006]It may be desirable to have cycloolefin-based compositions and
composites with characteristics that differ from those characteristics of
currently available cycloolefin-based compositions. It may be desirable
to have cycloolefin-based compositions and composites produced by methods
that differ from those methods currently available.

BRIEF DESCRIPTION

[0007]In one embodiment, a composition is provided that includes a
post-cured polymer. A post-cured polymer includes a reaction product of a
first cycloolefin and a metathesis catalyst having ruthenium, osmium, or
both ruthenium and osmium. The post-cured polymer has a glass transition
temperature in a range that is greater than 340 degrees Celsius.

[0008]In one embodiment, a composition is provided that includes a
post-cured polymer produced by metathesis polymerization of a first
cycloolefin initiated by a metathesis catalyst, and post-curing the
resulting polymer at a temperature that is greater than an onset
temperature for secondary curing of the polymer.

[0009]In one embodiment, a composition is provided that includes a
post-cured polymer. A post-cured polymer includes a reaction product of a
first cycloolefin and a metathesis catalyst. The post-cured polymer has a
glass transition temperature that is greater than 340 degrees Celsius,
and the post-cured polymer has an olefinic carbon content that is less
than about 35 percent.

[0010]In one embodiment, a method is provided that includes initiating a
metathesis polymerization of a first cycloolefin by a metathesis
catalyst. The resulting polymer is post-cured at a temperature that is
greater than an onset temperature for a secondary curing reaction of the
polymer.

[0016]The invention includes embodiments that relate to a
cycloolefin-based post-cured composition and article formed therefrom.
The invention includes embodiments that relate to a method of making the
cycloolefin-based post-cured composition and article.

[0017]In one embodiment, a composition is provided that includes a
post-cured polymer. A post-cured polymer includes a reaction product of a
first cycloolefin and a metathesis catalyst, and has a glass transition
temperature that is greater than 340 degrees Celsius. Glass transition
temperature as defined herein may be measured by Dynamic Mechanical
Analysis (DMA) on a resin bar (having dimensions of about 2
inch×0.5 inch×0.12 inch) in a TA Instruments RDA 3 model
fitted with a torsion rectangular fixture, operating at a frequency of 10
radians/second and a heating rate of 2 degrees Celsius/minute.

[0018]A post-cured polymer includes a reaction product of a cured polymer
that has been subjected to a post-curing reaction. Curing, as used
herein, may refer to a reaction resulting in polymerization,
cross-linking, or both polymerization and cross-linking of a curable
material. A curable material (for example, cycloolefin) may refer to a
material having one or more reactive groups (for example,
metathesis-active bonds in the cycloolefin) that may participate in a
chemical reaction when exposed to one or more of thermal energy,
electromagnetic radiation, or chemical reagents.

[0019]In one embodiment, curing may refer to ring opening of the
metathesis-active double bonds of the cycloolefin to form a cured
polymer. Cured polymer may refer to a polycycloolefin wherein more than
about 50 percent of the metathesis-active bonds have reacted by ROMP, or
alternatively a percent conversion of the metathesis active bonds is in a
range that is greater than about 50 percent. Percent conversion may refer
to a percentage of the total number of reacted groups (ring-opened double
bonds) to the total number of reactive groups (ring double bonds).

[0020]In one embodiment, a percent conversion of the metathesis-active
bonds in the cured polymer may be in a range that is greater than about
60 percent, greater than about 70 percent, greater than about 80 percent,
greater than about 90 percent, or greater than about 99 percent. In one
embodiment, a percent conversion of the metathesis-active bonds in the
cured polymer may be in a range of about 100 percent.

[0021]In one embodiment, a cured polymer may be characterized by a ratio
of the olefinic carbon to the aliphatic carbon in the cured polymer, or
alternatively percentage olefinic carbon content in the cured polymer
relative to the total carbon content (olefinic and aliphatic carbon). In
one embodiment, a cured polymer may have a ratio of the olefinic carbon
to the aliphatic carbon that is greater than about 4:6. In one
embodiment, a cured polymer may have a percentage olefinic carbon content
that is greater than about 40 percent. In one embodiment, a percentage
olefinic carbon content may be determined by 13C NMR spectroscopy.
FIG. 1 shows an example of a cured polymer formed by ROMP of
dicyclopentadiene having a ratio of olefinic to aliphatic carbon in a
range of about 4:6.

[0022]Post-curing, as used herein, may refer to a reaction resulting in a
secondary curing reaction of a cured polymer when exposed to one or more
of thermal energy, electromagnetic radiation, or chemical reagents.
Post-cured polymer, as used herein, may refer to a reaction product of a
cured polymer that has undergone a secondary curing reaction. In one
embodiment, a post-cured polymer may include a reaction product of a
cured polymer wherein more than about 40 percent of the olefinic carbon
in the cycloolefin has reacted, or alternatively a post-cured polymer may
have a percent olefinic carbon content in a range that is less than about
40 percent.

[0023]In one embodiment, a composition is provided that includes a
post-cured polymer. A post-cured polymer includes a reaction product of a
first cycloolefin and a metathesis catalyst, and the post-cured polymer
has a glass transition temperature in a range that is greater than 340
degrees Celsius, and the post-cured polymer has an olefinic carbon
content in a range that is less than about 35 percent. In one embodiment,
a post-cured polymer may have a percent olefinic carbon content in a
range that is less than about 35 percent, that is less than about 30
percent, that is less than about 25 percent, or that is less than about
20 percent. In one embodiment, a post-cured polymer may include
crosslinked polymeric species derived from a first cycloolefin.

[0024]A post-cured polymer, as described herein, may be characterized by
one or more physical properties, for example, glass transition
temperature. In one embodiment, a post-cured polymer may have a glass
transition temperature in a range of from about 350 degrees Celsius to
about 360 degrees Celsius, from about 360 degrees Celsius to about 370
degrees Celsius, from about 370 degrees Celsius to about 380 degrees
Celsius, from about 380 degrees Celsius to about 390 degrees Celsius, or
from about 390 degrees Celsius to about 400 degrees Celsius. In one
embodiment, a post-cured polymer may have a glass transition temperature
in a range that is greater than about 400 degrees Celsius. In one
embodiment, a post-cured polymer may have a glass transition temperature
that is greater than a decomposition temperature of the post-cured
polymer as measured by dynamic mechanical analysis (DMA). Here and
throughout the specification and claims, range limitations may be
combined and/or interchanged. Such ranges as identified include all the
sub-ranges contained therein unless context or language indicates
otherwise.

[0025]In one embodiment, a post-cured polymer may be characterized by
improved high-temperature physical properties (for example, storage
modulus) when compared to a cured polymer. In one embodiment, a
post-cured polymer may have a storage modulus value in a range that is
greater than about 2×109 dynes/cm2 at about 350 degrees
Celsius, greater than about 3×109 dynes/cm2 at about 350
degrees Celsius, greater than about 4×109 dynes/cm2 at
about 350 degrees Celsius, greater than about 5×109
dynes/cm2 at about 350 degrees Celsius, or greater than about
6×109 dynes/cm2 at about 350 degrees Celsius.

[0026]In one embodiment, a post-cured polymer may have a storage modulus
value in a range that is greater than about 5×109
dynes/cm2 at about 250 degrees Celsius, that is greater than about
5×109 dynes/cm2 at about 275 degrees Celsius, that is
greater than about 5×109 dynes/cm2 at about 300 degrees
Celsius, that is greater than about 5×109 dynes/cm2 at
about 315 degrees Celsius, that is greater than about 5×109
dynes/cm2 at about 335 degrees Celsius, that is greater than about
5×109 dynes/cm2 at about 350 degrees Celsius, or that is
greater than about 5×109 dynes/cm2 at about 375 degrees
Celsius. Storage modulus may be measured by Dynamic Mechanical Analysis
(DMA) on a resin bar (2 inch×0.5 inch×0.12 inch) in a TA
Instruments RDA 3 model fitted with a torsion rectangular fixture at a
frequency of 10 radians/second and a heating rate of 2 degrees
Celsius/minute.

[0027]In one embodiment, a post-cured polymer may have a number average
molecular weight in a range from about 100000 grams per mole to about
250000 grams per mole, from about 250000 grams per mole to about 500000
grams per mole, or from about 500000 grams per mole to about 1000000
grams per mole. In one embodiment, a post-cured polymer may have a number
average molecular weight in a range that is greater than about 1000000
grams per mole.

[0028]In one embodiment, post-curing of a cured polymer may be effected by
heating a cured polymer at a temperature greater than an onset
temperature for secondary curing reaction of the polymer. In one
embodiment, an onset temperature for secondary curing of a cured polymer
may be in a range greater than about 325 degrees Celsius. In one
embodiment, a cured polymer may be post-cured at a temperature in a range
of from about 325 degrees Celsius to about 330 degrees Celsius, from
about 330 degrees Celsius to about 335 degrees Celsius, from about 335
degrees Celsius to about 340 degrees Celsius, from about 340 degrees
Celsius to about 345 degrees Celsius, or from about 345 degrees Celsius
to about 350 degrees Celsius. In one embodiment, a cured polymer is
post-cured at a temperature in a range that is greater than 350 degrees
Celsius and less than the decomposition temperature of the cured polymer.

[0029]In one embodiment, post-curing a polymer at a temperature that is
greater than an onset temperature for secondary curing may result in an
increase in glass transition temperature of a post-cured polymer by
greater than about 200 degrees Celsius relative to the glass transition
temperature of a cured polymer heated to a temperature less than the
onset temperature for the secondary curing reaction.

[0030]In one embodiment, a composition is provided that includes a
post-cured polymer produced by metathesis polymerization of a first
cycloolefin initiated by a metathesis catalyst, and post-curing the
resulting cured polymer at a temperature that is greater than an onset
temperature for secondary curing of a cured polymer.

[0031]As described hereinabove a post-cured polymer is a reaction product
of a first cycloolefin and a metathesis catalyst. A "cycloolefin" refers
to an organic molecule having as a moiety at least one non-aromatic
cyclic ring, and in which the non-aromatic ring has at least one
carbon-carbon double bond, and of those carbon-carbon double bonds at
least one is a metathesis-active double bond. A metathesis-active double
bond includes a bond that is capable of undergoing a metathesis reaction
in the presence of a metathesis catalyst. A metathesis reaction of an
olefin refers to a chemical reaction involving redistribution of alkene
bonds. In one embodiment, a metathesis-active double bond in the
cycloolefin is capable of undergoing a ring-opening metathesis
polymerization reaction in the presence of a metathesis catalyst. Within
the group of cycloolefins, a "first cycloolefin" refers to those
molecules that further have at least one carbon-carbon double bond that
is capable of undergoing a secondary curing reaction that is not a
metathesis reaction when subjected to the post-curing reaction
conditions.

[0032]In one embodiment, a metathesis-active double bond in a first
cycloolefin itself may be capable of undergoing a secondary curing
reaction after the redistribution of alkene bonds due to ROMP reaction of
a cycloolefin. In an alternate embodiment, a first cycloolefin may have
two or more carbon-carbon double bonds in the cyclic ring, and of those
carbon-carbon double bonds at least one may be a metathesis-active double
bond and at least one other may be capable of undergoing a secondary
curing reaction that is not a metathesis reaction. In one embodiment,
even though all of the double bonds in a first cycloolefin may, for
example, be metathesis-active there may be at least a difference in
activation energy from one double bond to another to allow for one
metathesis active double bond to the polymerized by ROMP and another
double bond to be polymerized by a secondary curing reaction. In one
embodiment, a first cycloolefin is only a monofunctional cycloolefin. A
monofunctional cycloolefin as used herein refers to a cycloolefin having
a single metathesis-active double bond.

[0033]In one embodiment, a first cycloolefin may include one or more
heteroatoms. A heteroatom is an atom other than carbon and hydrogen, and
may include the group 15, group 16, or group 17 atom of the periodic
table. In one embodiment, a heteroatom may include N, O, P, S, As, or Se
atoms. In one embodiment, a first cycloolefin may include one or more
functional groups either as substituents of a first cycloolefin or
incorporated into the carbon chain of a first cycloolefin. Suitable
functional groups may include one or more of alcohol, thiol, ketone,
aldehyde, ester, disulfide, carbonate, imine, carboxyl, amine, amide,
nitro acid, carboxylic acid, isocyanate, carbodiimide, ether, halogen,
quaternary amine, phosphate, sulfate, or sulfonate.

[0034]In one embodiment, a first cycloolefin may include a structure
having a formula (I):

##STR00001##

wherein "v" is 1, 2, 3, 4, 5, or 6; R1 is independently at each
occurrence hydrogen, a halogen atom, an aliphatic radical, a
cycloaliphatic radical, an aromatic radical, an alkoxy group, a hydroxy
group, an ether group, an aldehyde group, an ester group, a ketone group,
a thiol group, a disulfide group, an amine group, an amide group, a
quaternary amine group, an imine group, an isocyanate group, a carboxyl
group, a silanyl group, a phosphanyl group, a sulfate group, a sulfonate
group, a nitro group, or two or more R1 together form a
cycloaliphatic radical, an aromatic radical, an imide group, or a
divalent bond linking two carbon atoms; and Y is C(R2)2,
C═C(R2)2, Si(R2)2, O, S, NR2, PR2,
BR2, or AsR2, wherein R2 is independently at each
occurrence hydrogen, an aliphatic radical, a cycloaliphatic radical, or
an aromatic radical. Aliphatic radical, cycloaliphatic radical, and
aromatic radical may be defined as the following:

[0035]Aliphatic radical is an organic radical having at least one carbon
atom, a valence of at least one and may be a linear or branched array of
atoms. Aliphatic radicals may include heteroatoms such as nitrogen,
sulfur, silicon, selenium and oxygen or may be composed exclusively of
carbon and hydrogen. Aliphatic radical may include a wide range of
functional groups such as alkyl groups, alkenyl groups, alkynyl groups,
halo alkyl groups, conjugated dienyl groups, alcohol groups, ether
groups, aldehyde groups, ketone groups, carboxylic acid groups, acyl
groups (for example, carboxylic acid derivatives such as esters and
amides), amine groups, nitro groups and the like. For example, the
4-methylpent-1-yl radical is a C6 aliphatic radical comprising a
methyl group, the methyl group being a functional group, which is an
alkyl group. Similarly, the 4-nitrobut-1-yl group is a C4 aliphatic
radical comprising a nitro group, the nitro group being a functional
group. An aliphatic radical may be a haloalkyl group that includes one or
more halogen atoms, which may be the same or different. Halogen atoms
include, for example; fluorine, chlorine, bromine, and iodine. Aliphatic
radicals having one or more halogen atoms include the alkyl halides:
trifluoromethyl, bromodifluoromethyl, chlorodifluoromethyl,
hexafluoroisopropylidene, chloromethyl, difluorovinylidene,
trichloromethyl, bromodichloromethyl, bromoethyl, 2-bromotrimethylene
(e.g., --CH2CHBrCH2--), and the like. Further examples of
aliphatic radicals include allyl, aminocarbonyl (--CONH2), carbonyl,
dicyanoisopropylidene --CH2C(CN)2CH2--), methyl
(--CH3), methylene (--CH2--), ethyl, ethylene, formyl (--CHO),
hexyl, hexamethylene, hydroxymethyl (--CH2OH), mercaptomethyl
(--CH2SH), methylthio (--SCH3), methylthiomethyl
(--CH2SCH3), methoxy, methoxycarbonyl (CH3OCO--),
nitromethyl (--CH2NO2), thiocarbonyl, trimethylsilyl
((CH3)3Si--), t-butyldimethylsilyl, trimethoxysilylpropyl
((CH3O)3SiCH2CH2CH2--), vinyl, vinylidene, and
the like. By way of further example, a "C1-C30 aliphatic
radical" contains at least one but no more than 30 carbon atoms. A methyl
group (CH3--) is an example of a C, aliphatic radical. A decyl group
(CH3(CH2)9--) is an example of a C10 aliphatic
radical.

[0036]A cycloaliphatic radical is a radical having a valence of at least
one, and having an array of atoms, which is cyclic but which is not
aromatic. A cycloaliphatic radical may include one or more non-cyclic
components. For example, a cyclohexylmethyl group
(C6H11CH2--) is a cycloaliphatic radical, which includes a
cyclohexyl ring (the array of atoms, which is cyclic but which is not
aromatic) and a methylene group (the noncyclic component). The
cycloaliphatic radical may include heteroatoms such as nitrogen, sulfur,
selenium, silicon and oxygen, or may be composed exclusively of carbon
and hydrogen. A cycloaliphatic radical may include one or more functional
groups, such as alkyl groups, alkenyl groups, alkynyl groups, halo alkyl
groups, conjugated dienyl groups, alcohol groups, ether groups, aldehyde
groups, ketone groups, carboxylic acid groups, acyl groups (for example
carboxylic acid derivatives such as esters and amides), amine groups,
nitro groups and the like. For example, the 4-methylcyclopent-1-yl
radical is a C6 cycloaliphatic radical comprising a methyl group,
the methyl group being a functional group, which is an alkyl group.
Similarly, the 2-nitrocyclobut-1-yl radical is a C4 cycloaliphatic
radical comprising a nitro group, the nitro group being a functional
group. A cycloaliphatic radical may include one or more halogen atoms,
which may be the same or different. Halogen atoms include, for example,
fluorine, chlorine, bromine, and iodine. Cycloaliphatic radicals having
one or more halogen atoms include 2-trifluoromethylcyclohex-1-yl;
4-bromodifluoromethylcyclooct-1-yl; 2-chlorodifluoromethylcyclohex-1-yl;
hexafluoroisopropylidene 2,2-bis(cyclohex-4-yl)
(--C6H10C(CF3)2C6H10--);
2-chloromethylcyclohex-1-yl; 3 difluoromethylenecyclohex-1-yl;
4-trichloromethylcyclohex-1-yloxy;
4-bromodichloromethylcyclohex-1-ylthio; 2-bromoethylcyclopent-1-yl;
2-bromopropylcyclohex-1-yloxy (e.g.
CH3CHBrCH2C6H10--); and the like. Further examples of
cycloaliphatic radicals include 4-allyloxy cyclohex-1-yl; 4-amino
cyclohex-1-yl (H2C6H10--); 4-amino carbonyl cyclopent-1-yl
(NH2COC5H.sub.8--); 4-acetyloxy cyclohex-1-yl; 2,2-dicyano
isopropylidene bis(cyclohex-4-yloxy)
(--OC6H10C(CN)2C6H10O--); 3-methyl
cyclohex-1-yl; methylenebis (cyclohex-4-yloxy)
(--OC6H10CH2C6H10O--); 1-ethyl cyclobut-1-yl;
cyclopropylethenyl; 3-formyl-2-terahydro furanyl; 2-hexyl-5-tetrahydro
furanyl; hexamethylene-1,6-bis(cyclohex-4-yloxy)
(--OC6H10(CH2)6C6H10--); 4-hydroxy methyl
cyclohex-1-yl (4-HOCH2C6H10--);
4-mercaptomethylcyclohex-1-yl (4-HSCH2C6H10--); 4-methyl
thio cyclohex-1-yl (4-CH3SC6H10--); 4-methoxy
cyclohex-1-yl; 2-methoxy carbonyl cyclohex-1-yloxy
(2-CH3OCOC6H100--); 4-nitro methyl cyclohex-1-yl
(NO2CH2C6H10--); 3-trimethyl silyl cyclohex-1-yl;
2-t-butyl dimethyl silyl cyclopent-1-yl; 4-trimethoxy silyl ethyl
cyclohex-1-yl (e.g.
(CH3O)3SiCH2CH2C6H10--); 4-vinyl
cyclohexen-1-yl; vinylidene bis(cyclohexyl); and the like. The term "a
C3-C30 cycloaliphatic radical" includes cycloaliphatic radicals
containing at least three but no more than 10 carbon atoms. The
cycloaliphatic radical 2-tetrahydrofuranyl (C4H7O--) represents
a C4 cycloaliphatic radical. The cyclohexylmethyl radical
(C6H11CH2--) represents a C7 cycloaliphatic radical.

[0037]An aromatic radical is an array of atoms having a valence of at
least one and having at least one aromatic group. This may include
heteroatoms such as nitrogen, sulfur, selenium, silicon and oxygen, or
may be composed exclusively of carbon and hydrogen. Suitable aromatic
radicals may include phenyl, pyridyl, furanyl, thienyl, naphthyl,
phenylene, and biphenyl radicals. The aromatic group may be a cyclic
structure having 4n+2 "delocalized" electrons where "n" is an integer
equal to 1 or greater, as illustrated by phenyl groups (n=1), thienyl
groups (n=1), furanyl groups (n=1), naphthyl groups (n=2), azulenyl
groups (n=2), anthracenyl groups (n=3) and the like. The aromatic radical
also may include non-aromatic components. For example, a benzyl group may
be an aromatic radical, which includes a phenyl ring (the aromatic group)
and a methylene group (the non-aromatic component). Similarly a
tetrahydronaphthyl radical is an aromatic radical comprising an aromatic
group (C6H3) fused to a non-aromatic component
--(CH2)4--. An aromatic radical may include one or more
functional groups, such as alkyl groups, alkenyl groups, alkynyl groups,
haloalkyl groups, haloaromatic groups, conjugated dienyl groups, alcohol
groups, ether groups, thio groups, aldehyde groups, ketone groups,
carboxylic acid groups, acyl groups (for example carboxylic acid
derivatives such as esters and amides), amine groups, nitro groups, and
the like. For example, the 4-methylphenyl radical is a C7 aromatic
radical comprising a methyl group, the methyl group being a functional
group, which is an alkyl group. Similarly, the 2-nitrophenyl group is a
C6 aromatic radical comprising a nitro group, the nitro group being a
functional group. Aromatic radicals include halogenated aromatic radicals
such as trifluoromethylphenyl; hexafluoro isopropylidene
bis(4-phen-1-yloxy) (--OPhC(CF3)2PhO--); chloromethyl phenyl;
3-trifluorovinyl-2-thienyl; 3-trichloro methylphen-1-yl
(3-CCl3Ph--); 4-(3-bromoprop-1-yl)phen-1-yl
(BrCH2CH2CH2Ph--); and the like. Further examples of
aromatic radicals include 4-allyloxyphen-1-oxy; 4-aminophen-1-yl
(H2NPh--); 3-aminocarbonylphen-1-yl (NH2COPh--);
4-benzoylphen-1-yl; dicyano isopropylidene bis(4-phen-1-yloxy)
(--OPhC(CN)2PhO--); 3-methylphen-1-yl; methylene bis(phen-4-yloxy)
(--OPhCH2PhO--); 2-ethylphen-1-yl; phenylethenyl;
3-formyl-2-thienyl; 2-hexyl-5-furanyl;
hexamethylene-1,6-bis(phen-4-yloxy) (--OPh(CH2)6PhO--);
4-hydroxymethylphen-1-yl (4-HOCH2Ph--); 4-mercaptomethylphen-1-yl
(4-HSCH2Ph--); 4-thiophenyl (--S-Ph); 4-methylthiophen-1-yl
(4-CH3SPh--); 3-methoxyphen-1-yl; 2-methoxycarbonylphen-1-yloxy
(e.g., methyl salicyl); 2-nitromethylphen-1-yl (--PhCH2NO2);
3-trimethylsilylphen-1-yl; 4-t-butyldimethylsilylphenl-1-yl;
4-vinylphen-1-yl; vinylidenebis(phenyl); and the like. The term "a
C3-C30 aromatic radical" includes aromatic radicals containing
at least three but no more than 30 carbon atoms. The aromatic radical
1-imidazolyl (C3H2N2--) represents a C3 aromatic
radical. The benzyl radical (C7H7--) represents a C7
aromatic radical.

[0038]In one embodiment, a first cycloolefin may include two or more
cyclic rings that may be fused with each other. In one embodiment, a
first cycloolefin may include Diels-Alder adducts of two or more
cyclopentadienes. In one embodiment, a first cycloolefin may include
Diels-Alder adducts of cyclopentadiene and oligocyclopentadienes. In one
embodiment, a first cycloolefin may include functionalized or
unfunctionalized dicyclopentadiene.

[0039]In one embodiment, a first cycloolefin may include a structure
having a formula (II)

##STR00002##

wherein "p" is an integer from 0 to 100; "w" is 1 or 2; "x" is 1, 2, 3, or
4; R3 and R4 are independently at each occurrence hydrogen, a
halogen atom, an aliphatic radical, a cycloaliphatic radical, an aromatic
radical, an alkoxy group, a hydroxy group, an ether group, an aldehyde
group, an ester group, a ketone group, a thiol group, a disulfide group,
an amine group, an amide group, a quaternary amine group, an imine group,
an isocyanate group, a carboxyl group, a silanyl group, a phosphanyl
group, a sulfate group, a sulfonate group, a nitro group; and Z is
C(R5)2, C═C(R5)2, Si(R5)2, O, S,
NR5, PR5, BR5, or AsR5, wherein R5 is
independently at each occurrence hydrogen, an aliphatic radical, a
cycloaliphatic radical, or an aromatic radical.

[0040]In one embodiment, a first cycloolefin may include one or more of
dicyclopentadiene, norbornene, oxanorbornene, norbornadiene,
cyclooctadiene, cyclooctene, cyclotetraene, cyclodecene, cyclododecene,
or a derivative thereof. In one embodiment, a first cycloolefin may
include dicyclopentadiene.

[0041]In one embodiment, a composition may include a post-cured polymer
having a reaction product of a curable composition. In one embodiment, a
curable composition may include a first cycloolefin and a metathesis
catalyst, wherein cycloolefin and first cycloolefin are as defined
hereinabove. In one embodiment, a curable composition may include a first
cycloolefin, a second cycloolefin, and a metathesis catalyst. In one
embodiment, a second cycloolefin may be a monofunctional cycloolefin that
is different from a first cycloolefin.

[0042]In one embodiment, a second cycloolefin may include one or more
heteroatoms (for example, oxanorbornene). In one embodiment, a second
cycloolefin may include one or more functional groups either as
substituents of a second cycloolefin or incorporated into the carbon
chain of a second cycloolefin. Suitable functional groups may include one
or more of alcohol, thiol, ketone, aldehyde, ester, disulfide, carbonate,
imine, carboxyl, amine, amide, nitro acid, carboxylic acid, isocyanate,
carbodiimide, ether, halogen, quaternary amine, phosphate, sulfate or
sulfonate.

[0043]In one embodiment, a second cycloolefin may ring open polymerize
when contacted to a metathesis catalyst. In one embodiment, a second
cycloolefin may copolymerize with a first cycloolefin when contacted to a
metathesis catalyst. In one embodiment, a post-cured polymer may include
crosslinked polymeric species derived from a first cycloolefin, a second
cycloolefin, or both first cycloolefin and second cycloolefin. In one
embodiment, a post-cured polymer may include a reaction product of
mixtures of cycloolefins chosen to provide the desired end-use
properties.

[0044]In one embodiment, one or more functional properties of a post-cured
polymer produced using the mixtures of cycloolefins may be determined by
the type of functional groups present and the number of functional groups
present.

[0045]A first cycloolefin may be present in an amount greater than about
0.5 weight percent based on the combined weight of the composition. In
one embodiment, a first cycloolefin may be present in an amount in a
range of from about 0.5 weight percent to about 1 weight percent of the
combined weight of the composition. In one embodiment, a first
cycloolefin may be present in an amount in a range of from about 1 weight
percent to about 5 weight percent of the combined weight of the
composition, from about 5 weight percent to about 10 weight percent of
the combined weight of the composition, from about 10 weight percent to
about 25 weight percent of the combined weight of the composition, or
from about 25 weight percent to about 50 weight percent of the combined
weight of the composition. In one embodiment, a first cycloolefin may be
present in an amount that is greater than about 50 weight percent of the
combined weight of the composition. In embodiments involving mixtures of
cycloolefins, the combined weight of the cycloolefins may be present in
an amount in a range of from about 0.5 weight percent to about 50 weight
percent of the combined weight of the composition.

[0046]In one embodiment, a metathesis catalyst may include a transition
metal catalyst. In one embodiment, a metathesis catalyst may include a
tungsten or a molybdenum salt. In one embodiment, a metathesis catalyst
may include a tungsten halide or a tungsten oxyhalide, activated by an
alkyl aluminum compound.

[0047]In one embodiment, a metathesis catalyst may include ruthenium,
osmium, or both ruthenium and osmium. In one embodiment, ruthenium or
osmium may form a metal center of the catalyst. In one embodiment, Ru or
Os in the catalyst may be in the +2 oxidation state, may have an electron
count of 16, and may be penta-coordinated. In an alternate embodiment, Ru
or Os in the catalyst may be in the +2 oxidation state, may have an
electron count of 18, and may be hexa-coordinated.

[0048]In one embodiment, a metathesis catalyst may include a structure
having a formula (III):

##STR00003##

wherein "a" and "b" are independently integers from 1 to 3, with the
proviso that "a+b" is less than or equal to 5;M is ruthenium or osmium;X
is independently at each occurrence an anionic ligand;L is independently
at each occurrence a neutral electron donor ligand;R6 is hydrogen,
an aliphatic radical, a cycloaliphatic radical, or an aromatic
radical;R7 is an aliphatic radical, a cycloaliphatic radical, an
aromatic radical, or S--R8; or R6 and R7 together form a
cycloaliphatic radical or an aromatic radical; andR8 is an aliphatic
radical, a cycloaliphatic radical, or an aromatic radical.

[0049]A metathesis catalyst may include one or more neutral
electron-donating ligand, one or more anionic ligand, and an alkylidene
radical as shown hereinabove in formula (III). A neutral
electron-donating ligand, an anionic ligand or an alkylidene radical may
be bonded to the metal center by coordination bond formation. As used
herein, the term "neutral electron-donating ligand" refers to ligands
that have a neutral charge when removed from the metal center. As used
herein the term "alkylidene radical" refers to a substituted or
unsubstituted divalent organic radical formed from an alkane by removal
of two hydrogen atoms from the same carbon atom, the free valencies of
which are part of a double bond. In one embodiment, a carbon atom in the
alkylidene radical may form a double bond with the metal center in the
metal complex. A carbon atom in the alkylidene radical may be substituted
with R6 and R7, wherein R6 and R7 are as defined
hereinabove.

[0050]An anionic ligand X in formula (III) may be a unidentate ligand or
bidentate ligand. In one embodiment, X in formula (III) may be
independently at each occurrence a halide, a carboxylate, a sulfonate, a
sulfonyl, a sulfinyl, a diketonate, an alkoxide, an aryloxide, a
cyclopentadienyl, a cyanide, a cyanate, a thiocyanate, an isocyanate, or
an isothiocyanate. In one embodiment, X in formula (III) may be
independently at each occurrence chloride, fluoride, bromide, iodide,
CF3CO2, CH3CO2, CFH2CO2,
(CH3)3CO, (CF3)2(CH3)CO,
(CF3)(CH3)2CO, PhO, MeO, EtO, tosylate, mesylate, or
trifluoromethanesulfonate.

[0051]The number of anionic ligands X bonded to the metal center may
depend on one or more of the coordination state of the transition metal
(for example, penta-coordinated or hexa-coordinated), the number of
neutral electron donating ligands bonded to the transition metal, or
dentency of the anionic ligand. In one embodiment, X in formula (III) may
include a unidentate anionic ligand and "b" may be 2. In one embodiment,
X in formula (III) may include a bidentate anionic ligand and "b" may be
1. In one embodiment, X in formula (III) may be independently at each
occurrence a chloride and "b` may be 2.

[0052]In one embodiment, an electron donor ligand L in formula (III) may
be independently at each occurrence a monodentate, a bidentate, a
tridentate, or a tetradentate neutral electron donor ligand. In one
embodiment, at least one L may be phosphine, phosphite, phosphinite,
phosphonite, arsine, stibine, ether, amine, amide, imine, sulfoxide,
carboxyl, nitrosyl, or thioethene. In one embodiment, at least one L may
be a phosphine having formula P(R9R10R11), where R9,
R10, and R11 are each independently an aliphatic radical, a
cycloaliphatic radical, or an aromatic radical. In one embodiment, at
least L may include P(cyclohexyl)3, P(cyclopentyl)3,
P(isopropyl)3, or P(phenyl)3.

[0053]In one embodiment, at least one L may be a heterocyclic ligand. A
heterocyclic ligand refers to an array of atoms forming a ring structure
and including one or more heteroatoms as part of the ring, where
heteroatoms are as defined hereinabove. A heterocyclic ligand may be
aromatic (heteroarene ligand) or non-aromatic, wherein a non-aromatic
heterocyclic ligand may be saturated or unsaturated. A heterocyclic
ligand may be further fused to one or more cyclic ligand, which may be a
heterocycle or a cyclic hydrocarbon, for example in indole.

[0054]In one embodiment, at least one L may be a heteroarene ligand. A
heteroarene ligand refers to an unsaturated heterocyclic ligand in which
the double bonds form an aromatic system. In one embodiment, at least one
L is furan, thiophene, pyrrole, pyridine, bipyridine, picolylimine,
gamma-pyran, gamma-thiopyran, phenanthroline, pyrimidine, bipyrimidine,
pyrazine, indole, coumarone, thionaphthene, carbazole, dibenzofuran,
dibenzothiophene, pyrazole, imidazole, benzimidazole, oxazole, thiazole,
dithiazole, isoxazole, isothiazole, quinoline, bisquinoline,
isoquinoline, bisisoquinoline, acridine, chromene, phenazine,
phenoxazine, phenothiazine, triazine, thianthrene, purine, bisimidazole,
or bisoxazole. In one embodiment, at least one L may be a monodentate
heteroarene ligand, which may be unsubstituted or substituted, for
example, pyridine. In one embodiment at least one L may be a bidentate
heteroarene ligand, which may be substituted or unsubstituted, for
example, bipyridine, phenanthroline, bithiazole, bipyrimidine, or
picolylimine.

[0055]In one embodiment, at least one L may be a N-heterocyclic carbene
ligand (NHC). A N-heterocyclic carbene ligand is a heterocyclic ligand
including at least one N atom in the ring and a carbon atom having a free
electron pair. Examples of NHC ligands may include ligands of formula
(IV), (V), or (VI)

##STR00004##

wherein R12, R13, R14, R15, R16, or R17 may
be independently at each occurrence hydrogen, an aliphatic radical, a
cycloaliphatic radical, or an aromatic radical. In one embodiment,
R14, R15, R16, and R17 may be independently at each
occurrence hydrogen. In one embodiment, R12 and R13 may be
independently at each occurrence a substituted or an unsubstituted
aromatic radical.

[0057]The number of neutral electron donor ligands L bonded to the
transition metal may depend on one or more of the coordination state of
the transition metal (for example, penta-coordinated or
hexa-coordinated), the number of anionic ligands bonded to the transition
metal, or dentency of the neutral electron donor ligand. In one
embodiment, "a" in formula (III) may be 1. In one embodiment, "a" in
formula (III) may be 2. In one embodiment, "a" in formula (III) may be 3.
In one embodiment, R6, R7, X and L may be bound to one another
in an arbitrary combination to form a multidentate chelate ligand. In one
embodiment two or more of R6, R7, X or L may independently form
a cyclic ring, for example, R6 and R7 may together form a
substituted or unsubstituted indene group.

[0058]In one embodiment, at least one L in formula (III) may include a
phosphine ligand. In one embodiment, at least one L in formula (III) may
include P(cyclohexyl)3, P(cyclopentyl)3, P(isopropyl)3, or
P(phenyl)3. In one embodiment, at least one L in formula (III) may
include a monodentate pyridine ligand, which is unsubstituted or
substituted. In one embodiment, at least one L in formula (III) may
include a bromine-substituted monodentate pyridine ligand. In one
embodiment, at least one L in formula (III) may include a N-heterocyclic
carbene ligand (NHC). In one embodiment, at least one L in formula (III)
may include an NHC ligands having formula (IV), (V), or (VI).

[0059]In one embodiment, R7 in formula (III) may include an aromatic
radical. In one embodiment, R7 in formula (III) may include a
substituted or an unsubstituted benzyl radical. In one embodiment, at
least one X in formula (III) may include a halide. In one embodiment, at
least one X in formula (III) may include a chloride.

[0061]The metathesis catalyst may be present in an amount greater than
about 0.001 weight percent based on the combined weight of the
composition. In one embodiment, a metathesis catalyst may be present in
an amount in a range of from about 0.001 weight percent to about 0.002
weight percent of the combined weight of the composition, from about
0.002 weight percent to about 0.005 weight percent of the combined weight
of the composition, or from about 0.005 weight percent to about 0.01
weight percent of the combined weight of the composition. In one
embodiment, a metathesis catalyst may be present in an amount in a range
of from about 0.01 weight percent to about 0.02 weight percent of the
combined weight of the composition, from about 0.02 weight percent to
about 0.03 weight percent of the combined weight of the composition, from
about 0.03 weight percent to about 0.05 weight percent of the combined
weight of the composition, or from about 0.05 weight percent to about 0.1
weight percent of the combined weight of the composition. In one
embodiment, a metathesis catalyst may be present in an amount that is
greater than about 0.1 weight percent of the combined weight of the
composition.

[0062]In one embodiment, a metathesis catalyst may initiate a ring opening
metathesis polymerization reaction when contacted to a first cycloolefin
or a second cycloolefin. In one embodiment, the conversion of the
cycloolefin(s) may be complete, that is, the reaction product may be free
of any unreacted cycloolefin(s). In one embodiment, the conversion of the
cycloolefin(s) may be incomplete, that is, the reaction product may
include unreacted cycloolefin(s). In one embodiment, the conversion of
the cycloolefin(s) may be in a range that is greater than about 50 weight
percent. In one embodiment, the conversion of the cycloolefin(s) may be
in a range of from about 50 weight percent to about 60 weight percent,
from about 60 weight percent to about 70 weight percent, from about 70
weight percent to about 80 weight percent, from about 80 weight percent
to about 90 weight percent, or from about 90 weight percent to about 100
weight percent.

[0063]The curable composition may include a reaction control agent. A
reaction control agent may be added to control the pot life of the
reaction mixture. In one embodiment, a reaction control agent may include
a neutral electron donor or a neutral Lewis base. Suitable reaction
control agents may include one or more of phosphines, sulfonated
phosphines, phosphites, phosphinites, or phosphonites. Other suitable
reaction control agents may include one or more of arsines, stibines,
sulfoxides, carboxyls, ethers, thioethers, or thiophenes. Yet other
suitable reaction control agents may include one or more of amines,
amides, nitrosyls, pyridines, nitriles, or furans. In one embodiment, an
electron donor or a Lewis base may include one or more functional groups,
such as hydroxyl; thiol; ketone; aldehyde; ester; ether; amine; amide;
nitro acid; carboxylic acid; disulfide; carbonate; carboalkoxy acid;
isocyanate; carbodiimide; carboalkoxy; and halogen. In one embodiment, a
reaction control agent may include one or more of triphenylphosphine,
tricyclopentylphosphine, tricyclohexylphosphine, triphenylphosphite,
pyridine, propylamine, tributylphosphine, benzonitrile, triphenylarsine,
anhydrous acetonitrile, thiophene, or furan. In one embodiment, a
reaction control agent may include one or more of P(cyclohexyl)3,
P(cyclopentyl)3, P(isopropyl)3, P(Phenyl)3, or pyridine.

[0064]Optionally, the curable composition may include one or more
additives. Suitable additives may be selected with reference to
performance requirements for particular applications. For example, a fire
retardant additive may be selected where fire retardancy may be desired,
a flow modifier may be employed to affect rheology or thixotropy, a
reinforcing filler may be added where reinforcement may be desired, and
the like. The additives may include one or more of flow control agents,
modifiers, carrier solvents, viscosity modifiers, adhesion promoters,
ultra-violet absorbers, flame-retardants, or reinforcing fillers.
Defoaming agents, dyes, pigments, and the like may also be incorporated
into composition. The amount of such additives may be determined by the
end-use application.

[0065]In one embodiment, an article is provided. An article includes a
filler and post-cured polymer. A post-cured polymer includes a reaction
product of a first cycloolefin and metathesis catalyst, and a post-cured
polymer has a glass transition temperature in a range that is greater
than 340 degrees Celsius.

[0066]A suitable filler may include one or more material selected from
siliceous materials, carbonaceous materials, metal hydrates, metal
oxides, metal borides, or metal nitrides. In one embodiment, the filler
essentially may include carbonaceous materials. The filler may be
particulate, fiberous, platelet, whiskers or rods, or a combination of
two or more of the foregoing.

[0067]The filler may include a plurality of particles. The plurality of
particles may be characterized by one or more of average particle size,
particle size distribution, average particle surface area, particle
shape, or particle cross-sectional geometry.

[0068]In one embodiment, an average particle size (average diameter) of
the filler may be less than about 1 nanometer. In one embodiment, an
average particle size of the filler may be in a range of from about 1
nanometer to about 10 nanometers, from about 10 nanometers to about 25
nanometers, from about 25 nanometers to about 50 nanometers, from about
50 nanometers to about 75 nanometers, or from about 75 nanometers to
about 100 nanometers. In one embodiment, an average particle size of the
filler may be in a range of from about 0.1 micrometers to about 0.5
micrometers, from about 0.5 micrometers to about 1 micrometer, from about
1 micrometer to about 5 micrometers, from about 5 micrometers to about 10
micrometers, from about 10 micrometers to about 25 micrometers, or from
about 25 micrometers to about 50 micrometers. In another embodiment, an
average particle size of the filler may be in a range of from about 50
micrometers to about 100 micrometers, from about 100 micrometers to about
200 micrometers, from about 200 micrometers to about 400 micrometers,
from about 400 micrometers to about 600 micrometers, from about 600
micrometers to about 800 micrometers, or from about 800 micrometers to
about 1000 micrometers. In one embodiment, an average particle size of
the filler may be in a range of greater than about 1000 micrometers.

[0069]In another embodiment, filler particles having two distinct size
ranges (a bimodal distribution) may be included in the composition: the
first range from about 1 nanometers to about 500 nanometers, and the
second range from about 0.5 micrometer (or 500 nanometers) to about 1000
micrometers (the filler particles in the second size range may be herein
termed "micrometer-sized fillers").

[0070]Filler particle morphology can be selected to include shapes and
cross-sectional geometries based on the process used to produce the
particles. In one embodiment, a filler particle may be a sphere, a rod, a
tube, a flake, a fiber, a plate, a whisker, or be part of a plurality
that includes combinations of two or more thereof. In one embodiment, a
cross-sectional geometry of the particle may be one or more of circular,
ellipsoidal, triangular, rectangular, or polygonal.

[0071]In one embodiment, the filler may be fibrous. A fibrous material may
include one or more fibers and may be configured as a thread, a strand,
yarn, a mat, a fabric, a woven roving, or a continuous filament. In one
embodiment, a fibrous material may include one or more fiber having high
strength. In one embodiment, a fibrous material may include continuous
fibers. In one embodiment, a fibrous material may include discontinuous
fibers. The strength of the fibers may be further increased by forming a
plurality of layers or plies, by orientation of the fibers in a
direction, and like methods.

[0072]With further reference to the material suitable to form the fibers,
glass, ceramic, metal, and cermet are suitable. Suitable examples of
glass fibers may include E-glass or S-glass fiber. Suitable examples of
fibers may include, but are not limited to, glass fibers (for example,
quartz, E-glass, S-2 glass, R-glass from suppliers such as PPG, AGY, St.
Gobain, Owens-Corning, or from Johns Manville).

[0073]With regard to fibers that are carbonaceous, a suitable fiber may
include a polymer. Suitable polymers may include one or more of
polyester, polyamide (for example, NYLON polyamide available from E.I.
DuPont, Wilmington, Del.), aromatic polyamide (such as KEVLAR aromatic
polyamide available from E.I. DuPont; or P84 aromatic polyamide available
from Lenzing Aktiengesellschaft, Austria), polyimide (for example, KAPTON
polyimide available from E.I. DuPont,), or polyolefins. Suitable
polyolefins may include extended chain polyethylene (for example, SPECTRA
polyethylene from Honeywell International Inc., Morristown, N.J.; or
DYNEEMA polyethylene from Toyobo Co., Ltd., Tokyo, Japan), and the like.

[0075]In one embodiment, the filler may include aggregates or agglomerates
prior to incorporation into the composition, or after incorporation into
the composition. An aggregate may include more than one filler particle
in physical contact with one another, while an agglomerate may include
more than one aggregate in physical contact with one another. In some
embodiments, the filler particles may not be strongly agglomerated and/or
aggregated such that the particles may be relatively easily dispersed in
the polymeric matrix.

[0076]Optionally, the filler may be subjected to mechanical or chemical
processes to improve the dispersibility of the filler in the polymer
matrix. In one embodiment, the filler may be subjected to a mechanical
process, for example, high shear mixing prior to dispersing in the
polymer matrix. In one embodiment, the filler may be chemically treated
prior to dispersing in the polymeric matrix.

[0077]Chemical treatment may include removing polar groups from one or
more surfaces of the filler particles to reduce aggregate and/or
agglomerate formation. Chemical treatment may also include
functionalizing one or more surfaces of the filler particles with
functional groups that may improve the compatibility between the fillers
and the polymeric matrix, reduce aggregate and/or agglomerate formation,
or both improve the compatibility between the fillers and the polymeric
matrix and reduce aggregate and/or agglomerate formation. In some
embodiments, chemical treatment may include applying a sizing composition
to one or more surface of the filler particles.

[0078]In one embodiment, an article may include a coupling agent
composition. A coupling agent composition is capable of bonding to a
filler having a corresponding binding site. As used herein, the term
"coupling agent" refers to a material that may provide for an improved
interface or adhesion between the filler and a polymeric material.

[0079]The filler binding sites may include functional groups that may
react or interact with the coupling agent composition to result in bond
formation. As described hereinabove, in some embodiments, binding sites
may be capable of covalent bond formation with the coupling agent
composition. In other embodiments, binding sites may be capable of
physical bond formation with the coupling agent composition, for example,
van der Waals interactions or hydrogen bonding.

[0080]In one embodiment, suitable binding sites may be intrinsic to the
filler, that is, present in the filler because of filler chemistry or
processing steps involved in filler fabrication. In one embodiment,
suitable binding sites may be included in the filler extrinsically, for
example, by chemical treatment post-filler fabrication. In one
embodiment, suitable binding sites in the filler may include both
intrinsic and extrinsic functional groups. In one embodiment, a filler
may include a sizing composition and the sizing composition may include
one or more binding sites capable of bonding with the coupling agent
composition. In one embodiment, suitable binding sites may include one or
more of epoxy groups, amine groups, hydroxyl groups, or carboxylic
groups.

[0081]In one embodiment, a filler may be present in amount in a range of
less than about 10 weight percent of the article. In one embodiment, a
filler may be present in amount in a range of from about 10 weight
percent to about 20 weight percent of the article, from about 20 weight
percent to about 30 weight percent of the article, from about 30 weight
percent to about 40 weight percent of the article, or from about 40
weight percent to about 50 weight percent. In one embodiment, a filler
may be present in amount in a range of from about 50 weight percent to
about 55 weight percent of the article, from about 55 weight percent to
about 65 weight percent of the article, from about 65 weight percent to
about 75 weight percent of the article, from about 75 weight percent to
about 95 weight percent of the article, or from about 95 weight percent
to about 99 weight percent of the article. In one embodiment, a filler
may be essentially present in amount in a range of from about 20 weight
percent to about 80 weight percent of the article. In one embodiment, a
filler may be essentially present in amount in a range of from about 40
weight percent to about 80 weight percent of the article.

[0082]In one embodiment, the coupling agent composition may be mixed in
with the polymer precursor to form the curable composition. The curable
composition may be then contacted with the filler. In one embodiment, a
filler may include a fibrous material placed in a cavity of a mold. A
curable material may be dispensed into the mold to impregnate the fibrous
material.

[0083]In one embodiment, rather than mixing the coupling agent into the
curable composition with the other ingredients, the coupling agent
composition may be contacted with filler by coating the filler surface by
dipping the fillers in a solution of the coupling agent composition or by
spraying the fillers with a solution of the coupling agent composition.
Solutions of coupling agent compositions if employed may include solvents
having sufficiently volatility to allow for evaporation of the solvent.
In one embodiment, a coupling agent composition maybe contacted with the
filler using solid-state deposition techniques. If aqueous coupling
agents are desired to be used, the aqueous coupling agents can be
emulsified to form a water in oil (WO) emulsion. Other emulsions, OW,
WOW, and OWO emulsions may be used where appropriate.

[0084]In one embodiment, an article fabricated employing the compositions
and methods disclosed herein may have a thickness that is greater than
about 0.1 millimeters, greater than about 0.5 millimeters, greater than
about 1 millimeters, greater than about 0.5 centimeters, greater than
about 1 centimeter, greater than about 5 centimeters, or greater than
about 10 centimeters.

[0085]In one embodiment, a laminate is provided. A laminate may include
two or more layers. In one embodiment at least one layer may include a
post-cured polymer. A post-cured polymer may include a reaction product
of a filler having binding sites and a curable composition including a
coupling agent composition (if present), a first cycloolefin, a second
cycloolefin (if present) and a metathesis catalyst. In one embodiment,
the two or more layers may be bonded to each other. In one embodiment, a
laminate may include at least one adhesive layer bonding the two or more
layers.

[0086]In one embodiment, a cured composite structure is provided. A cured
composite structure may include a filler and a post-cured polymer as
described herein.

[0087]A cured composite structure may have mechanical properties, thermal
properties, or chemical properties depending on the end-use requirements.
In one embodiment, a cured resin in the composite structure may have a
tensile modulus in a range of from about 250,000 pounds per square inch
(psi) to about 300,000 pounds per square inch (psi), from about 300,000
pounds per square inch (psi) to about 400,000 pounds per square inch
(psi), from about 400,000 pounds per square inch (psi) to about 500,000
pounds per square inch (psi), from about 500,000 pounds per square inch
(psi) to about 600,000 pounds per square inch (psi), or from about
600,000 pounds per square inch (psi) to about 700,000 pounds per square
inch (psi).

[0088]Compression strength for the composite structure may be measured
using ASTM method D6641. In one embodiment, the composite structure may
include a fibrous material and the fibers may be present in a direction
parallel to the load during the test (0 degrees) and perpendicular to the
load direction during the test (90 degrees direction). In one embodiment,
a cured composite structure made with half the fibers in the 0 degree
direction and half in the 90 degree direction may have a compression
strength in a range of from about 30 kilo pounds per square inch (ksi) to
about 40 kilo pounds per square inch (ksi), from about 40 kilo pounds per
square inch (ksi) to about 50 kilo pounds per square inch (ksi), from
about 50 kilo pounds per square inch (ksi) to about 60 kilo pounds per
square inch (ksi), from about 60 kilo pounds per square inch (ksi) to
about 70 kilo pounds per square inch (ksi), from about 70 kilo pounds per
square inch (ksi) to about 80 kilo pounds per square inch (ksi), from
about 80 kilo pounds per square inch (ksi) to about 90 kilo pounds per
square inch (ksi), or from about 90 kilo pounds per square inch (ksi) to
about 100 kilo pounds per square inch (ksi).

[0089]Toughness value for the composite structure may be measured using
ASTM D5528-01 method for Mode I and an internally developed test using
end-notch-flexure technique for Mode II. In one embodiment, the cured
composite structure may have a toughness value in Mode I in a range of
from about 2 pounds per inch to about 5 pounds per inch, from about 5
pounds per inch to about 10 pounds per inch, from about 10 pounds per
inch to about 15 pounds per inch, or from about 15 pounds per inch to
about 20 pounds per inch. In one embodiment, the cured composite
structure may have a toughness value in Mode II in a range of from about
5 pounds per inch to about 10 pounds per inch, from about 10 pounds per
inch to about 20 pounds per inch, from about 20 pounds per inch to about
30 pounds per inch, from about 30 pounds per inch to about 40 pounds per
inch, or from about 40 pounds per inch to about 50 pounds per inch.

[0090]In one embodiment, a cured composite structure may be chemically
resistant. In one embodiment, a cured composite structure may exhibit
chemical resistance desired for the specific end-use. In one embodiment,
chemical resistance may be defined as less than 15 percent reduction in
compression strength after exposure to chemicals such as methyl ethyl
ketone, acids, hydraulic fluids such as Skydrol, detergent, or engine
fuels.

[0091]In one embodiment, a method is provided. A method includes
initiating a metathesis polymerization of a first cycloolefin by a
metathesis catalyst. In one embodiment, a method may include initiating a
ring opening metathesis polymerization reaction of a first cycloolefin, a
second cycloolefin, or both the first cycloolefin and the second
cycloolefin.

[0092]In one embodiment, a method may include heating a curable
composition including the cycloolefin(s) and the metathesis catalyst to
form a cured polymer, wherein cured polymer is as described hereinabove.
In one embodiment, a curable composition may be heated to a first
temperature in a range of from about 20 degrees Celsius to about 30
degrees Celsius, from about 30 degrees Celsius to about 40 degrees
Celsius, from about 40 degrees Celsius to about 50 degrees Celsius, from
about 50 degrees Celsius to about 60 degrees Celsius, or from about 60
degrees Celsius to about 75 degrees Celsius. In one embodiment, a curable
composition including the cycloolefin(s) and the metathesis catalyst may
be heated to a first temperature for a sufficient duration of time such
that a cured polymer is formed.

[0093]The method includes post-curing the resulting polymer at a
temperature that is greater than an onset temperature for secondary
curing of the polymer. In one embodiment, the cured polymer may be
post-cured at a temperature in a range of from about 325 degrees Celsius
to about 330 degrees Celsius, from about 330 degrees Celsius to about 335
degrees Celsius, from about 335 degrees Celsius to about 340 degrees
Celsius, from about 340 degrees Celsius to about 345 degrees Celsius, or
from about 345 degrees Celsius to about 350 degrees Celsius. In one
embodiment, a cured polymer may be post-cured at a temperature in a range
that is greater than 350 degrees Celsius and less than the decomposition
temperature of the cured polymer. In one embodiment, a cured polymer may
be post-cured for a sufficient duration of time such that a post-cured
polymer is formed.

[0094]In one embodiment, a method may include contacting a filler with a
curable composition including a coupling agent composition (if present),
a first cycloolefin, a second cycloolefin (if present), and a metathesis
catalyst. In one embodiment, a filler may include a fibrous material
placed in a cavity of a mold. A curable composition may be dispensed into
the mold to impregnate the fibrous material. In one embodiment, a method
may include impregnating a fibrous material with a curable composition
including a first cycloolefin and a metathesis catalyst.

[0095]In one embodiment, a method may include fabricating the curable
composition into an article of a desired shape or size by a molding
technique. In one embodiment, a molding technique may include one or more
of resin transfer molding (RTM), reaction injection molding (RIM),
structural reaction injection molding (SRIM), vacuum-assisted resin
transfer molding (VARTM), thermal expansion transfer molding (TERM),
resin injection recirculation molding (RICM), controlled atmospheric
pressure resin infusion (CAPRI) or Seeman's composite resin infusion
molding (SCRIMP). In one embodiment, a method may essentially include
fabricating the article by resin infusion method. In one embodiment, a
method may essentially include fabricating the article by vacuum-assisted
resin transfer molding.

EXAMPLES

[0096]The following examples only illustrate methods and embodiments in
accordance with the invention, and do not impose limitations upon the
clauses. Unless specified otherwise, all ingredients are commercially
available from such common chemical suppliers as Alpha Aesar, Inc. (Ward
Hill, Mass.), or Sigma-Aldich Co. (St. Louis, Mo.).

[0097]An amount that is 8.5 milligrams of
1,3-Bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene) dichloro
(phenylmethylene) (tricyclohexylphosphine) ruthenium is dissolved in 0.45
grams of toluene before being mixed with 8.51 grams of dicyclopentadiene
at 35 degrees Celsius. A sample of the resulting mixture is transferred
to a differential scanning calorimeter (DSC) instrument (heating rate of
10° C./min) and the resulting thermogram is shown in FIG. 2. An
onset temperature for ROMP reaction is observed about 49 degrees Celsius
with a peak exotherm at about 52 degrees Celsius. The ROMP reaction is
complete below 150 degrees Celsius and no further reaction is observed
before 300 degrees Celsius. A second exothermic reaction is observed
having an onset temperature greater than about 325 degrees Celsius.

Example 2

Post-Cure Reaction of DCPD as a Function of Temperature

[0098]An amount that is 1 weight part of
1,3-Bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene) dichloro
(phenylmethylene) (tricyclohexylphosphine) ruthenium is dissolved in
approximately 50 parts of toluene. This solution is added to 1000 parts
of melted DCPD at a temperature of about 35 degrees Celsius. After
thorough mixing using a magnetic stirrer the mixture is poured into a
teflon coated tray and allowed to gel at room temperature. The samples
are placed in an oven at about 50 degrees Celsius and heated to a
temperature of about 100 degrees Celsius at 10° C./minute. The
samples are held at a temperature of 100 degrees Celsius for 10 minutes
prior to removal from the oven. Post-cure under air is achieved by
placing the samples in a forced air oven at the designated temperature
for 5 minutes. Post-cure under nitrogen is achieved by placing the
samples in an autoclave, evacuating the autoclave and refilling with
nitrogen. The autoclave is then heated to the designated temperature and
held for 20 minutes before cooling down the autoclave and removing the
samples. The samples are then cut into 2 inch×0.5 inch strips for
analysis by DMA using a band saw; the edges are sanded down to a smooth
finish. Table 1 lists the post-cure conditions for Samples 1 to 7.

[0099]Resin bars (having dimensions of approximately 2 inch×0.5
inch×0.12 inch) of Samples 1 to 7 are prepared as described above
in Example 2. Mechanical properties of the resin bars are measured by
Dynamic Mechanical Analyses (DMA) in a TA Instruments RDA 3 model fitted
with a torsion rectangular fixture at a frequency of 10 radians/second
and a heating rate of 2 degrees Celsius/minute.

[0100]FIG. 3 shows the DMA plots for storage modulus as a function of
temperature for Samples 1 to 7. FIG. 3 shows that the glass transition
temperature (Tg) for the post-cured samples is dependent on cure
conditions (for example, air or N2). FIG. 3 also shows that the
Tg for samples post-cured at temperatures greater than 250 degrees
Celsius is higher than Tg observed for samples post-cured at 250
degrees Celsius or lower. Sample 5, post-cured at a temperature of 350
degrees Celsius does not show any glass transition temperature even at
temperatures greater than 350 degrees Celsius or at temperatures below
the decomposition temperature (around 400 degrees Celsius).

[0101]FIG. 4 shows the Tg values measured as a function of post-cure
temperature for Samples 1 to 7. FIG. 4 shows an almost step change in the
Tg once a particular post-cure temperature is reached. An intercept
of the best-fit curves for the two Tg regimes is observed at about
325 degrees Celsius indicating that an onset temperature for the
secondary cure reaction may be greater than about 325 degrees Celsius.

Example 4

Percentage Olefinic Content in the Post-Cured DCPD Samples

[0102]The amount of percentage olefinic content in the post-cured DCPD
samples 1, 3, and 5 is determined by solid state 13C NMR
spectroscopy. FIG. 5 shows the 13C NMR spectra for samples 1, 3, and
5. Table 2 lists the percentage olefinic and carbon content as measured
by 13C NMR and shows that the percentage olefinic content in
post-cured DCPD is almost the same as that of a cured DCPD that has not
undergone a further crosslinking reaction (about 40 percent). Table 2
further shows that the percentage olefinic content in post-cured DCPD
decreases when post-cured at 300 degrees Celsius and further decreases to
less than about 30 percent when post-cured at 350 degrees Celsius.

[0103]Reference is made to substances, components, or ingredients in
existence at the time just before first contacted, formed in situ,
blended, or mixed with one or more other substances, components, or
ingredients in accordance with the present disclosure. A substance,
component or ingredient identified as a reaction product, resulting
mixture, or the like may gain an identity, property, or character through
a chemical reaction or transformation during the course of contacting, in
situ formation, blending, or mixing operation if conducted in accordance
with this disclosure with the application of common sense and the
ordinary skill of one in the relevant art (e.g., chemist). The
transformation of chemical reactants or starting materials to chemical
products or final materials is a continually evolving process,
independent of the speed at which it occurs. Accordingly, as such a
transformative process is in progress there may be a mix of starting and
final materials, as well as intermediate species that may be, depending
on their kinetic lifetime, easy or difficult to detect with current
analytical techniques known to those of ordinary skill in the art.

[0104]Reactants and components referred to by chemical name or formula in
the specification or claims hereof, whether referred to in the singular
or plural, may be identified as they exist prior to coming into contact
with another substance referred to by chemical name or chemical type
(e.g., another reactant or a solvent). Preliminary and/or transitional
chemical changes, transformations, or reactions, if any, that take place
in the resulting mixture, solution, or reaction medium may be identified
as intermediate species, master batches, and the like, and may have
utility distinct from the utility of the reaction product or final
material. Other subsequent changes, transformations, or reactions may
result from bringing the specified reactants and/or components together
under the conditions called for pursuant to this disclosure. In these
other subsequent changes, transformations, or reactions the reactants,
ingredients, or the components to be brought together may identify or
indicate the reaction product or final material.

[0105]In the specification and the claims, reference will be made to a
number of terms that have the following meanings. The singular forms "a",
"an" and "the" include plural referents unless the context clearly
dictates otherwise. Approximating language, as used herein throughout the
specification and claims, may be applied to modify any quantitative
representation that could permissibly vary without resulting in a change
in the basic function to which it is related. Accordingly, a value
modified by a term such as "about" is not to be limited to the precise
value specified. In some instances, the approximating language may
correspond to the precision of an instrument for measuring the value.
Similarly, "free" may be used in combination with a term, and may include
an insubstantial number, or trace amounts, while still being considered
free of the modified term.

[0106]As used herein, the terms "may" and "may be" indicate a possibility
of an occurrence within a set of circumstances; a possession of a
specified property, characteristic or function; and/or qualify another
verb by expressing one or more of an ability, capability, or possibility
associated with the qualified verb. Accordingly, usage of "may" and "may
be" indicates that a modified term is apparently appropriate, capable, or
suitable for an indicated capacity, function, or usage, while taking into
account that in some circumstances the modified term may sometimes not be
appropriate, capable, or suitable. For example, in some circumstances an
event or capacity can be expected, while in other circumstances the event
or capacity can not occur--this distinction is captured by the terms
"may" and "may be".

[0107]The foregoing examples are illustrative of some features of the
invention. The appended claims are intended to claim the invention as
broadly as has been conceived and the examples herein presented are
illustrative of selected embodiments from a manifold of all possible
embodiments. Accordingly, it is Applicants' intention that the appended
claims not limit to the illustrated features of the invention by the
choice of examples utilized. As used in the claims, the word "comprises"
and its grammatical variants logically also subtend and include phrases
of varying and differing extent such as for example, but not limited
thereto, "consisting essentially of" and "consisting of:" Where
necessary, ranges have been supplied, and those ranges are inclusive of
all sub-ranges there between. It is to be expected that variations in
these ranges will suggest themselves to a practitioner having ordinary
skill in the art and, where not already dedicated to the public, the
appended claims should cover those variations. Advances in science and
technology may make equivalents and substitutions possible that are not
now contemplated by reason of the imprecision of language; these
variations should be covered by the appended claims.